Emulsions of water-insoluble organic acid-fading inhibitors dissolved in water-insoluble organic solvents



Patented Mar. 27, 1951 EMULSIONS OF WATER-INSOLUBLE OR- GANIC ACID-FADING INHIBITORS DIS- SOLVED IN WATER-INSOLUBLE ORGANIC SOLVENTS 'William 1. Hart, Dover, and Victor S. Salvin,

Irvington, N. 1., assignors to Celanese Corporation of America, a corporation of Delaware No Drawing. Application .luly'3,1'94 8, Serial No. 37,094

7 Claims.

This invention relates to the treatment of dyed organic derivatives of cellulose textile materials, and relates more particularly to a novel treatment for organic derivative of cellulose textile materials dyed with dyestuffs having a tendency to fade when expos d to an acid atmosphere, whereby said fading is inhibited.

An object of this invention is to provide an improved process for the treatment of colored cellulose acetate or other organic derivative of cellulose textile materials which .have been dyed with colors which are ot ordinarily fast to acid fumes whereby the resistance of said dyed textile materials to acid fading is substantially improved.

Another object of this invention is the provision of dyed c llulose acetate or other organic derivative of cellulose textile materials which are highly resistant to acid fading. and whose acid fading resistance is substantially permanent to Washing and dry cleaning.

Other objects of this invention will appear from the following detailed description.

In the coloration of textile materials it is very desirable that the colors produced on the materials be as fast as possible to light, washing and to other agencies such as acid fumes. Many dyestuifs yield on organic derivative of cellulose materials desirable colors which are fast to Washing but these colors often suffer from a lack of fastness to acid fumes. 'When fabrics to which these dyestuffs have been applied are exposed to acid fumes, such as, for example, the products of combustion of coal, gas, etc., the color undergoes a change in shade. This change is usually referred to as acid fading. The change which occurs may be a dulling of the brightness of the shade in some instances, and in others there may be a definite change in color. This undesirable effect is frequently observed in the case of many anthraquinone dyestuffs which yield valuable blue colors on organic derivative of cellulose materials. When fabrics dyed with these colors are exposed to acid fumes the colors change from a pure blue shade to one having a reddish cast. On continued exposure to the acid fumes the blue color may even change to a pink color. Such changes naturally restrict the range of usefulness of these dyestuffs. In order to overcome this tendency toward acid fading, the usegi various protective or acid-fading inhibiting agents has been suggested. While many of the agents do impart an appreciable degree of protection, the effect is usually not completely permanent since washing or dry-cleaning elimihates in. whole or in part the protective effect achieved. This appears to be due to the fact that by the usual methods of applying said organic acid fading inhibiting agents only a surface applicaton is realized and washing or dry cleaning remove said agents. Accordingly, more effective methods of increasing the resistance of these dyes to acid fading are of great commercial importance.

We have now found that the acid fading characteristics of dyed cellulose acetate or other organic derivative of cellulose textile materials which have been dyed with dyestuffs having a tendency to fade when exposed to the action of acid fumes may be substantially improved and the resistance to acid fading thus imparted is rendered substantially permanent to washing and dry cleaning if said dyed cellulose acetate or other organic derivative of cellulose textile material is treated with a stable aqueous emulsion of an organic acid fading inhibiting agent, which emulsion is formulated in a particular manner. In accordance with our novel process the stable aqueous emulsion We employ consists of a solution of said inhibiting agent in a water-insoluble organic solvent, said solution being dispersed in water with the aid of suitable dispersing agents, so that in the emulsion formed the droplets of the water-insoluble solvent solution of the inhibiting agent comprise the disperse phase and the water comprises the continuous phase of said emulsion.

As examples of inhibiting agents which we may employ in practicing the process of our invention, there may be mentioned diphenylethylene dianiine, NN-diphenylacetamidine, N methyl- NN' diphenylacetamidine, N e ethyl NN die phenylacetamidine, benzyl ethyl aniline, "phenyl morpholine, diphenyl guanidine, dibenzylethylenediamine, diphenylbenzamidine, benzimidoazole, 2-methyl-benzimidoazole and 1,3-diphenylimidazolidine.

The aqueous emulsions employed in accordance with our novel process preferably contain from 0.3 to 2.0% by weight of said inhibiting agent. The emulsion is preferably applied to the dyed organic derivative of cellulose textile material by padding operations, the nip of the padding mangle being so adjusted that sufficient liquid is retained on the fabric to deposit in a uniform fashion thereon from 0.3 to 2.0% on the weight of the fabric of the inhibiting agent after the organic liquid solvent and Water in which the latter is dispersed are removed and the treated fabric is dried. Drying of the padded fabric may be conveniently efiected at a temperature. of 570 to 150 C., the treated fabric being exposed to said temperature until the liquid present is evaporated, usually in from about 5 to about 20 minutes.

In order to form the aqueous emulsion which is applied to the dyed textile material, the inhibiting agent'which is employed is dissolved in a water-insoluble organic liquid solvent therefor containing a plurality of dispersing agents, at least one of which is a water-soluble anionic surface active agent and one which is a waterinsoluble, but oil-soluble, non-ionic surface active agent, and the organic solution obtained then dispersed in water with agitation to form the desirzd stabl aqueous emulsion. The emulsion thus obtained comprises a dispersion of droplets of an organic solution'of the inhibitor in water. The water-insoluble but oil-soluble 'the emulsion and acts as an auxiliary solvent for the amine inhibitor in the organic solv'nt while the water-soluble, anionic surface active agent stabilizes the emulsion of the water-insoluble droplets in the aqueous, continuous phase. In treating the textile material, the aqueous emulsion is preferably applied, as stated, by padding operations, although any other con venient method of application may be employed. 'When forming the emulsion, optimum results are obtained when the organic solution which is dispersed in water is formed by dissolving from about 5 to parts by weight of a water-soluble anionic surface active agent consisting, for example, of a highly sulfonated fatty acid ester, such as sulfcnated glyceryl triricinoleate, and from about 5 to 15 parts by weight of a non-ionic water-insoluble, but oil-soluble, surface active agent, such as the condensate of a polyethylene glycol, -i. e. a compound of the formula HO' (CH2CH2O)1LOH, wherein n is an integer of from 2 to 10, with a long chain fatty ac d, for example, oleic acid, in 50 to 90 parts by weight of a water-insoluble organic solvent such as toluene, xylene, isopropyl ether, dibutyl ether, dihexyl ether, beta-beta'-dichlor-diethyl ether, glycol dioleate or benzene, for example. From 10 to 20 parts by weight of dioxan, ethyl alcohol,

diacetone alcohol or acetone may then be added thereto to increase the solvent power of the mixture for the inhibiting agent. Advantageously, from about 10 to 20 parts by weight of a watermiscible condensate of a polyethyltne glycol with a long chain aliphatic alcohol, such as laur'yl alcohol, may also be added to the organic solvent solution to aid in stabilizing the emulsion. About 10 to 20 parts by weight of the desiredinhibiting agent are then dissolved in about 30 parts by weight of the organic solution of dispersing agents thus formed by adding the amine to the solution and heating the mixture to about '75 to 80 C. The solution of the amine thus obtai-nedis then dispersed with stirring in about 1000*parts by weight of water so as to form-the desired aqueous emulsion which is applied to the dyed textile material.

The application of acid fading inhibitors on dyed textile materials in the specific emulsion form in which we apply said inhibitors yields a degree of protection which is quite outstanding. 1 Textile materials treated by our novel emulsion method retain their resistance to acid fading even after said materials are washed or subjected to dry cleaning operations.

Our novel proclss of applying said inhibiting agents in the specific emulsion form described,

4 acts to cause said inhibiting agents to enter the filaments or fibers comprising the textile material in the manner of dyestuffs. Due to the actual absorption of the inhibiting agents, the protective effect obtained is substantially permanent and unaffected by washing or dry cleaning.

In order further to illustrate our invention, but without being limited thereto, the following examples are given:

Example I A solution of dispersing agents is formed by dissolving 10 parts by weight of completely sulfonatad glyceryl triricinoleate, 10 parts by weight of the monolauryl ether of a polyethylene glycol 0f the general formula HOCHiCHP-O (CI-ICHzO) nC1zH25 wherein n is 2, 10 parts by weight of the dioleate of a polyethylene glycol, such as dodecaethylene glycol, and 10 parts by weight of dioxan in 60 parts by weight of toluene. 10 parts by weight of diphenylethylenediamine are dissolved in 30 parts by weight of the above solution by warming the latter to to C. and the resulting solution then poured into 970 parts by weight of water with stirring. An emulsion of organic liquid droplets in water is formed by further stirring at high speed. The average particle size of the amine is thus reduced to about 1 micron or less.

A cellulose acetate fabric dyed in a blue shade with 1:4 dimethylamino anthraquinone is padded with the above emulsion, the nip of the padding mangle being so adjusted that the fabric retains an equal weight of liquid. The impregnated fabric is then dried by heating at 80 to C. for about l5 minutes. About 1% on the weight ofthe dyed fabric of diplienylethylenediamine is thus deposited thereon. The treated dyed fabric has a resistance to acid fading of 2 units in accordance with the standard A. A. T. C. 0. test while untreated dyed fabric has an acid fading resistance of only 0 units. The treated fabric retains its resistance to acid fading even after being washed or dry cleaned.

Example II An aqueous emulsion containing 1% by weight of diphenylacetarnidine is prepared in the man ner described in Example I. When padded onto a cellulose acetate fabric dyed in a blue shade with 1:e-dimethylamino-anthraquinone so as to deposit uniformly thereon 1% by weight of diphenylacetamidine, the treated dyed fabric obtained exhibits a resistance to acid fading of 1.5 units in accordance with the standard A. A. T. C. C. test. As indicated above, .untreated dyed fabric has a resistance to acid fading of but 0 units.

Example III An aqueous emulsion containing 1% by weight of 1,3-diphenylimidazolidine is prepared in the manner described in Examplelfi When padded on to a fabric dyed in a blue-green shade with lA-diethanolamino 5,8 dihydroxy-anthraquinone so as to deposit 1% by weight of said inhibitor thereon, th treated dyed fabric exhibits an acid fading resistance of 2 units in accordance with the standard A. A. T. C. C. test. Untreated dyed fabric has a resistance of 0 units. While our invention has been more particularly described. in connection with the treatment" of cellulose acetate textile materials, equally satisfactory results are obtained when said textile materials have a basis of other organic derivatives of cellulose such as other organic acid esters and ethers of cellulose. Examples of other organic acids esters of cellulose are cellulose propionate, cellulose butyrate, cellulose acetate propionate and cellulose acetate butyrate, while examples of cellulose ethers are ethyl cellulose and benzyl cellulose.

It is to be understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of our invention.

Having described our invention, what we desire to secure by Letters Patent is:

1. Process for improving the fastness of colorations on dyed organic derivative of cellulose textile material to acid fading, which comprises treating said dyed organic derivative of cellulose textile material with a stable emulsion comprising a dispersion in Water of a solution in a waterinsoluble organic solvent of a water-insoluble organic acid fading inhibiting agent, said emulsion being formed by dissolving a plurality of dispersing agents in the organic solvent employed, at least one of which dispersing agents is a watersoluble anionic surface active agent and one a water-insoluble but oil-soluble non-ionic surface active agent, adding the inhibiting agent thereto, dissolving it therein and dispersing the resulting organic solution in water.

2. Process for improving the fastness of colorations on dyed cellulose acetate textile material to acid fading, which comprises treating said dyed cellulose acetate textile material with a stable emulsion comprising a dispersion in water of a solution in a water-insoluble organic solvent of a water-insoluble organic acid fading inhibiting agent, said emulsion being formed by dissolving a plurality of dispersing agents in the organic solvent employed, at least one of which dispersing agents is a water-soluble anionic surface active agent and one a water-insoluble but oil-solublenondonic surface active agent, adding the inhibiting agent thereto, dissolving it therein and dispersing the resulting organic solution in water.

3. Process for improving the fastness of colorations on dyed organic derivative of cellulose textile materials to acid fading, which comprises treating said dyed organic derivative of cellulose textile materials with a stable emulsion comprising a dispersion in water of a solution of a water-insoluble organic acid fading inhibiting agent in toluene, said emulsion being prepared by dissolving a plurality of dispersing agents in toluene, at least one of which dispersing agents is a water-soluble anionic surface active agent and one a water-insoluble but oil-soluble non-ionic surface active agent, adding the inhibiting agent thereto, dissolving it therein and dispersing the resulting organic solution in water.

4. Process for improving the fastness of colorations on dyed organic derivative of cellulose textile materials to acid fading, which comprises treating said dyed organic derivative of cellulose textile materials with a stable emulsion comprising a dispersion in water of a solution of a water-insoluble organic acid fading inhibiting agent in toluene, said emulsion being prepared by dissolving sulfonated glyceryl riclnoleate, a water-insoluble, oil-soluble dioleate of a polyethylene glycol and the mono-lauryl ether of a polyethylene glycol in toluene, adding the inhibiting agent thereto, dissolving it therein, and dispersing the resulting organic solution in water.

5. Process for improving the fastness of colorations on dyed cellulose acetate textile materials to acid fading, which comprises treating said dyed cellulose acetate textile materials with a stable emulsion comprising a dispersion in water of a solution of a water-insoluble organic acid fading inhibiting agent in toluene and dioxan, said emulsion being prepared by dissolving sulfonated glyceryl ricinoleate, a water-insoluble, oil-soluble dioleate of a polyethylene glycol and the mono-lauryl ether of a polyethylene glycol in a mixture of toluene and dioxan, adding the inhibiting agent thereto, dissolving it therein, and dispersing the resulting organic solution in water.

6. Process for improving the fastness of colorations on dyed cellulose acetate textile materials to acid fading, which comprises treating said dyed cellulose acetate materials with a stable emulsion comprising a dispersion in water of a solution of a water-insoluble organic acid fading inhibiting agent in toluene and ethyl alcohol, said emulsion being prepared by dissolving sulfonated glyceryl ricinoleate, a water-insoluble, oilsoluble dioleate of a polyethylene glycol and the mono-lauryl ether of a polyethylene glycol in a mixture of toluene and ethyl alcohol, adding the inhibiting agent thereto, dissolving it therein, and dispersing the resulting organic solution in water.

7. Process for improving the fastness of colorations on dyed cellulose acetate textile materials to acid fading, which comprises treating said dyed cellulose acetat materials with a suitable emulsion comprising a dispersion in water of a solution of a' water-insoluble organic acid fading inhibiting agent, in toluene and ethyl alcohol, said emulsion being prepared by dissolving 5 to 15 parts by weight of sulfonated glyceryl triric- 'inoleate, 5 to 15 parts by weight of a waterinsoluble, oil-soluble dioleate of a polyethylene glycol and 10 to 20 parts by weight of the-monolauryl ether of a polyethylene glycol in a mixture of 50 to parts by weight of toluene containing 10 to 20 parts by weight of ethyl alcohol, adding 10 to 20 parts by weight of the desired inhibiting agent thereto, dissolving it therein and dispersing the resulting organic solution in water.

WILLIAM J. HART. VICTOR S. SALVIN'.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Journal of the Am. Pharm. Assoc. (Scientific Edition) for Feb. 1945, pages 56, 5'7, 58.

Atlas Spans and Atlas Tweens, published by Atlas Powder Co., Wilmington, Del., Nov. 1942, pages 5 and 8. 

1. PROCESS FOR IMPROVING THE FASTNNESS OF COLORATIONS ON DYED ORGANIC DERIVATIVE OF CELLULOSE TEXTILE. MATERIAL TO ACID FADING, WHICH COMPRISES TREATING SAID DYED ORGANIC DERIVATIVE OF CELLULOSE TEXTILE MATERIAL WITH A STABLE EMULSION COMPRISING A DISPERSION IN WATER OF A SOLUTION IN A WATERINSOLUBLE ORGANIC SOLVENT OF A WATER-INSOLUBLE ORGANIC ACID FADING INHIBITING AGENT, SAID EMULSION BEING FORMED BY DISSOLVING A PLURALITY OF DISPERSING AGENTS IN THE ORGANIC SOLVENT EMPLOYED, AT LEAST ONE OF WHICH DISPERSING AGENTS IS A WATERSOLUBLE ANIONIC SURFACE ACTIVE AGENT AND ONE A WATER-INSOLUBLE BUT OIL-SOLUBLE NON-IONIC SURFACE ACTIVE AGENT, ADDING THE INHIBITING AGENT THERETO, DISSOLVING IT THEREIN AND DISPERSING THE RESULTING ORGANIC SOLUTION IN WATER. 